US6063876A - Epoxy resin composition and epoxy resin composition for encapsulating semiconductors - Google Patents
Epoxy resin composition and epoxy resin composition for encapsulating semiconductors Download PDFInfo
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- US6063876A US6063876A US09/085,209 US8520998A US6063876A US 6063876 A US6063876 A US 6063876A US 8520998 A US8520998 A US 8520998A US 6063876 A US6063876 A US 6063876A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to an epoxy resin composition which can be crushed at an ordinary temperature, is remarkably low in melt viscosity, and which can provide excellent physical properties after curing. Also, the present invention relates to an epoxy resin composition for encapsulating semiconductors in which the above-mentioned epoxy resin composition is formulated, which is excellent in fluidity, and can provide a cured product having excellent solder crack resistance.
- Epoxy resins have been employed in a wide field such as adhesion, casting, encapsulating, laminating, molding, coating, etc. Because of the excellent physical properties after curing and ease in handling. Further, epoxy resin includes many kinds, and since physical properties after curing largely vary according to the selection, it has been separately employed according to use fields and purposes.
- epoxy resin compositions are employed for encapsulating semiconductors, requirements in properties are getting severer even in the field. That is, semiconductor devices become highly integrated owing to semiconductor chips having a remarkably large capacity, and packages themselves become small-sized and thin-sized. Still further, in the semiconductor devices, mounting also shifts to a surface-mounting, and the semiconductor devices in the surface mounting are directly immersed into a solder bath. Accordingly, those are exposed to a high temperature circumstance, and a large stress is wholly induced in the package because of abrupt expansion by absorbed moisture, and cracks are caused in encapsulants. For that reason, for the epoxy resin composition for encapsulants having excellent solder crack resistance, there are required a high heat resistance (that is, high glass transition temperatures), a low moisture absorption property, and a low stress property.
- Cresol-novolak type epoxy resins which are mainly employed at present time have not become regarded as sufficient in view of a low moisture absorption property and low melt viscosity.
- an epoxy resin having a softening point of not more than 55° C. is too soft and sticky to crush at an ordinary temperature. Therefore, it cannot be employed, or there are required specified apparatuses and conditions.
- an epoxy resin having a low molecular weight has low melt viscosity and, in the case of a usual noncrystalline epoxy resin, a softening point lowers with lowering of a molecular weight, and since it becomes semi-solid state or liquid, it cannot be crushed at an ordinary temperature.
- An object of the present invention is to provide an epoxy resin composition that can be crushed at an ordinary temperature, is low in melt viscosity, and can provide excellent physical properties after curing. Also, it is an object of the invention to provide a novel epoxy resin composition for encapsulating semiconductors in which the above-mentioned epoxy resin composition is mixed, and which can provide a cured product having excellent fluidity and solder crack resistance.
- the present inventors have found out that, by mixing a 4,4'-biphenol type epoxy resin with a noncrystalline epoxy resin having a low softening point, the mixture can be crushed at an ordinary temperature, and the object can be attained.
- the present invention relates to an epoxy resin composition which can be crushed at an ordinary temperature, said epoxy resin composition comprising:
- the 4,4'-biphenol type epoxy resin (a) which is one component in the epoxy resins employed in the epoxy resin composition of the present invention, is crystalline at an ordinary temperature, whereby it can be crushed, and it is very low in viscosity over the melting point thereof because of a low molecular weight. Further, it is rigid in the structure, whereby, it is excellent also in heat resistance. However, since the melting point is very high such as not less than 150° C., and it is also poor in compatibility with a curing agent, etc., it cannot be employed solely.
- an epoxy resin composition was prepared which satisfies all properties required for the use of the noncrystalline epoxy resin having a low melting point which cannot be solely employed because of being incapable of crushing, in addition to the 4,4'-biphenol type epoxy resin in a specified proportion.
- the 4,4'-biphenol type epoxy resin (a), which is one component in the epoxy resin composition of the present invention, is an epoxy resin prepared by condensation polymerization of 4,4'-biphenol with epihalohydrin in the presence of alkalis.
- n is preferably 0 to 0.5, and more preferably 0 to 0.3 on an average in order to maintain crystallinity.
- the noncrystalline epoxy resin (b) having a softening point of 35° C. to 55° C. which is another component in the epoxy resin composition, is not particularly limited so far as it is noncrystalline and has a softening point of 35° C. to 55° C.
- epoxy resins prepared by various phenols and epihalohydrin epoxy resins prepared by amines such as diaminodiphenylmethane, aminophenol, xylenediamine and epihalohydrin
- epoxy resins prepared by various carboxylic acids such as methylhexahydroxy phthalic acid and a dimer acid and epihalohydrin.
- the various phenols include phenols such as bisphenol A, bisphenol F, bisphenol AD, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, methylresorcin, dihydroxy diphenylether, dihydroxynaphthalene, phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, phenol aralkyl resin, terpenphenol resin, dicyclopentadienephenol resin, naphthol novolak resin, brominated bisphenol A, brominated phenol novolak resin, and phenol-based compounds such as polyvalent phenol resins which are obtained by condensation reaction of the various phenols with various aldehydes such as benzaldehyde, hydroxy benzaldehyde, croton aldehyde, and glyoxal.
- phenols such as bisphenol A, bisphenol F, bisphenol AD, hydroquinone, methylhydroquinone, di
- the various epoxy resins may be employed solely or in combinations of two or more kinds. In the case of employing in combinations of two or more kinds, the respective epoxy resins do not always require noncrystallinity and a softening point of 35° C. to 55° C. If a mixed resin shows noncrystallinity and a softening point of 35° C. to 55° C., it can be employed as the noncrystalline epoxy resin (b) having a softening point of 35° C. to 55° C. which is one component in the epoxy resin composition of the present invention.
- noncrystalline epoxy resins (b) there is preferred a noncrystalline epoxy resin having a softening point of 35° C. to 55° C. composed of at least one kind of epoxy resin obtained by reaction of epihalohydrin with at least one kind of phenol compound selected from the group consisting of bisphenol A, bisphenol F, phenol-novolak resin, cresol-novolak resin, phenol-aralkyl resin, terpenephenol resin, dicyclopentadiene phenol resin, phenolcyclohexanone resin, and phenol benzaldehyde resin, and phenol compound represented by the general formulae (I) to (IV), in view of properties after curing, etc. ##STR2##
- the R 1 s may be identical or different, each denoting an alkyl group having a carbon number of 1 to 10, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, an alkoxy group, or a halogen atom.
- k is from 0 to 8 on an average
- the m 1 s may be identical or different, each denoting an integer of from 0 to 3.
- the Zs may be identical or different, each denoting a divalent group represented by general formulae (V) to (IX) described below.
- each R 2 and R 3 may be identical or different, each denoting a hydrogen atom, an alkyl group having a carbon number of 1 to 5, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, an alkoxy group, or a halogen atom, and m 2 is an integer from 0 to 4; ##STR4## wherein, each R 4 may be identical or different, each denoting an alkyl group having a carbon number of 1 to 5, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, an alkoxy group, or a halogen atom, and m 3 is an integer from 0 to 6; ##STR5## wherein, each R 5 and R 6 may be identical or different, each denoting a hydrogen atom, an alkyl group having a carbon number of 1 to 5, a substituted or unsubstituted phen
- a measurement of a softening point was conducted by a ring and ball method (JIS K7234) in the present invention. Further, crushing was conducted with a usual crusher such as a hammer mill, a ball mill, feather mill, a pulverizer, a jet mill, etc., so that average particle size was adjusted to 10 ⁇ to 500 ⁇ or so.
- a usual crusher such as a hammer mill, a ball mill, feather mill, a pulverizer, a jet mill, etc.
- the reaction of the phenol compounds with the epihalohydrin can be carried out by publicly known methods, and examples in typical embodiments are described below in detail. Firstly, the phenol compounds are dissolved into 3 to 20 mol of the epihalohydrin based on 1 mol of a phenolic hydroxyl group in the phenol compounds to prepare a uniform solution. Subsequently, while agitating the solution, the reaction is carried out by addition of 0.9 to 2 mol of an alkaline metal hydroxide based on 1 mol of phenolic hydroxyl group in the form of solid or aqueous solution. The reaction can be carried out under an ordinary pressure or a reduced pressure, and the reaction temperature is usually approximately 30° C. to 105° C.
- reaction liquid is optionally azeotropically evaporated while maintaining a fixed temperature, and a condensate obtained by cooling evaporated vapor is separated into oil/water, and then water is removed from a reaction system by a method in which an oily component removed from a water component is circulated into the reaction system.
- the alkaline metal hydroxide is intermittently or continuously supplied over 1 to 8 hours in order to suppress an abrupt reaction. Total reaction period is usually 1 to 10 hours.
- insoluble salts by-produced are removed by filtration or water washing, followed by distilling out for removing unreacted epihalohydrin under a reduced pressure to obtain an aimed epoxy resin.
- epichlorohydrin or epibromohydrin is usually employed, and as the alkaline metal hydroxide, NaOH or KOH is usually employed.
- a catalyst which includes quaternary ammonium salts such as tetraethylammonium chloride and tetraethyl ammonium bromide, tertiary amines such as benzylmethyl amine and 2,4,6-(trisdimethylaminomethyl)phenol, imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole, and phosphonium salts such as ethyltriphenyl phosphoniumiodide, and phosphines such as triphenyl phosphine.
- quaternary ammonium salts such as tetraethylammonium chloride and tetraethyl ammonium bromide
- tertiary amines such as benzylmethyl amine and 2,4,6-(trisdimethylaminomethyl)phenol
- imidazoles such as 2-ethyl-4-methylimidazole and 2-phen
- an inert organic solvent which includes alcohols such as ethanol and isopropanol, ketones such as acetone and methylethylketone, ethers such as dioxane and ethyleneglycol dimethylether, glycol ethers such as ethyleneglycol monomethylether, ethyleneglycol monobutylether, and propyleneglycol monomethylether, dimethyl sulfoxide, and dimethylformamide, which are an aprotic polar solvent.
- alcohols such as ethanol and isopropanol
- ketones such as acetone and methylethylketone
- ethers such as dioxane and ethyleneglycol dimethylether
- glycol ethers such as ethyleneglycol monomethylether, ethyleneglycol monobutylether, and propyleneglycol monomethylether
- dimethyl sulfoxide dimethylformamide
- the epoxy resin obtained as described hereinabove contains a too large amount of saponifiable halogens
- a refined epoxy resin having a sufficiently small amount of saponifiable halogens by repeated treatments. That is, a crude epoxy resin is dissolved again into an inert organic solvent such as isopropanol, methylethyl ketone, methylisobutyl ketone, toluene, xylene, dioxane, propyleneglycol monomethylether, dimethylsulfoxide, etc., and a ring-closing reaction is carried out again at a temperature of approximately 30° C. to 120° C.
- an inert organic solvent such as isopropanol, methylethyl ketone, methylisobutyl ketone, toluene, xylene, dioxane, propyleneglycol monomethylether, dimethylsulfoxide, etc.
- the 4,4'-biphenol type epoxy resin (a) and the noncrystalline epoxy resin (b) may be employed by mixing after separately preparing or obtaining, and those may be employed as a mixture of respective epoxy resins which are prepared by allowing to simultaneously react a mixture composed of the 4,4'-biphenol and the phenol resin which are respective raw materials of the noncrystalline epoxy resin with the epihalohydrin.
- the latter method is more preferred.
- the former method it is preferred to cool the mixture to an ordinary temperature after completely mixed at a melting state by heating, and to crush.
- the use proportion of the respective raw materials is controlled in advance so that the proportion of the mixture of the 4,4'-biphenol type epoxy resin (a) and the noncrystalline epoxy resin (b) is adjusted to a fixed proportion, or it is required to be adjusted by adding either epoxy resin after epoxidation to adjust to a fixed proportion.
- the 4,4'-biphenol type epoxy resin (a) is mixed with the noncrystalline epoxy resin (b) in a proportion of 20 to 90 parts by weight of the noncrystalline epoxy resin (b) based on 10 to 80 parts by weight of the 4,4'-biphenol type epoxy resin (a), and preferably 40 to 85 parts by weight of the noncrystalline epoxy resin (b) based on 15 to 60 parts by weight of the 4,4'-biphenol type epoxy resin (a).
- the 4,4'-biphenol type epoxy resin (a) is not more than 10 parts by weight, though the resin mixture is excellent in compatibility and physical properties in curing, it is poor in a property in crushing.
- the resin mixture is excellent in fluidity, there is caused a problem that it is poor in compatibility.
- the noncrystalline epoxy resin (b) is not more than 20 parts by weight, though the resin mixture is excellent in fluidity, it is poor in compatibility and, in the case of not less than 90 parts by weight, though the resin mixture is excellent in compatibility and a physical property in curing, there is caused a problem that it is poor in a property in crushing.
- the epoxy resin composition of the present invention can be crushed at an ordinary temperature, and it is remarkably low in melt viscosity, and which can provide an excellent property after curing. Accordingly, it can be advantageously employed in a field such as a molding material for encapsulating semiconductors, powder coatings, and powdered insulation materials.
- the epoxy resin composition for encapsulating semiconductors of the present invention is an epoxy resin composition for encapsulating semiconductors which comprises the epoxy resin composition of the present invention with an inorganic filler and a curing accelerator as essential components, and there can be mixed and employed other epoxy resins except the 4,4'-biphenol type epoxy resin (a) and the noncrystalline epoxy resin (b).
- an epoxy resin which is crystalline at an ordinary temperature prepared by epihalohydrin and a phenol compound such as 3,3'5,5'-tetramethyl-4-4'-biphenol, 4,4'-dihydroxy diphenylmethane, 3,3'5,5'-tetramethyl-4-4'dihydroxy diphenyl methane, hydroquinone, dibutylhydroquinone, and dihydroxydiphenyl ether, and a noncrystalline solid epoxy resin having a softening point exceeding 55° C.
- phenol compounds which include bisphenol A, bisphenol F, bisphenol AD, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, methylresorcin, dihydroxydiphenylether, dihydroxynaphthalene, phenol-novolak resin, cresol-novolak resin, bisphenol A novolak resin, phenolaralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, phenolcyclohexanone resin, phenolbenzaldehyde resin, naphthol novolak resin, brominated bisphenol A, brominated phenol novolak resin, etc., and various phenol compounds such as a polyvalent phenol resin obtained by condensation reaction of various phenol compounds with various aldehydes such as hydroxybenzaldehyde, croton aldehyde, and glyoxal.
- various phenol compounds such as a polyvalent phenol resin obtained by condensation reaction of various
- the other epoxy resins are employed in a proportion of preferably not more than 100 parts by weight, and more preferably not more than 50 parts by weight based on 100 parts by weight of the total amount of the 4,4'-biphenol type epoxy resin (a) and the noncrystalline epoxy resin (b). In the case that the other epoxy resins are employed in a proportion of not less than 100 parts by weight, an effect in the present invention is not sufficiently shown.
- a curing agent for epoxy resins are formulated as an essential component, and as the curing agent for epoxy resins, usual curing agents for epoxy resins can be employed without being particularly limited.
- phenols such as bisphenol A, bisphenol F, bisphenol AD, hydroquinone, resorcin, methyllesorcin, biphenol, tetramethylbiphenol, dihydroxy naphthalene, dihydroxy diphenylether, phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, dicyclopentadiene phenol resin, terpene phenol resin, phenol aralkyl resin, naphthol novolak resin, brominated bisphenol A, and brominated phenol novolak resin, various phenol resins such as a polyvalent phenol resin which is obtained by condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, croton aldehyde, and glyoxal, active ester compounds obtained by esterification in which phenolic hydroxyl groups in the various phenols (res)
- the phenol aralkyl resin the terpene phenol resin, the dicyclopentadiene phenol resin, and active ester-modified phenol resins obtained by complete or partial esterification of the phenolic hydroxyl groups in the various phenol resins in view of physical properties after curing, etc.
- the amount of the curing agent for epoxy resins to be employed in the epoxy resin composition for encapsulating semiconductors of the present invention is preferably 0.5 to 2.0 mol, more preferably 0.7 to 1.2 mol as the total groups capable of reacting with epoxy groups in the total curing agent for epoxy resins based on 1 mol of epoxy groups in the total components of the epoxy resins.
- an inorganic filler is formulated.
- the kind of the inorganic filler there are exemplified, for example, fused silica, crystalline silica, glass powder, alumina, and calcium carbonate, etc.
- the shape thereof is a crushed type or spherical.
- the various inorganic fillers are employed solely or as a mixture of at least two kinds and, of those, the fused silica and the crystalline silica are more preferred.
- the use amount is 70 to 95% by weight, preferably 80 to 93% by weight, and more preferably 85 to 92% by weight based on the total weight of the composition.
- the curing accelerator to be employed in the epoxy resin composition for encapsulating semiconductors of the present invention is a compound which is capable of accelerating reaction of epoxy groups in the epoxy resin with active groups in the curing agent.
- the curing accelerator there are exemplified, for example, phosphine compounds such as tributyl phosphine, triphenyl phosphine, tris(dimethoxyphenyl)phosphine, tris(hydroxypropyl)phosphine, tris(cyanoethyl)phosphine, phosphonium salts such as tetraphenylphosphonium phenyl borate, methyltributylphosphonium tetraphenylborate, methyltricyanoethylphosphonium tetraphenylborate, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole,
- phosphine compounds Of the compounds which are employed as the curing accelerator, there are preferred the phosphine compounds, imidazole compounds, diazabicyclo compounds, and the salts thereof.
- the curing accelerator is employed solely or as a mixture of two or more kinds, and the amount is 0.1 to 7% by weight, more preferably 1 to 5% by weight based on the epoxy resins.
- the epoxy resin composition for encapsulating semiconductors of the present invention there can be optionally formulated coupling agents, plasticizers, and pigments.
- antimony trioxide, phosphoric acid, etc. can be properly formulated.
- the epoxy resin composition for encapsulating semiconductors of the present invention is excellent in fluidity, and further, since it can provide a cured product having excellent solder crack resistance, it can be advantageously employed in a field of encapsulating semiconductors.
- the present invention is illustrated in more detail based on Preparation Examples for respective epoxy resins employed in the epoxy resin composition of the present invention, Examples for the epoxy resin composition of the present invention, Crushing Examples and Comparative Examples for the respective epoxy resins and the respective epoxy resin compositions and, further, Examples and Comparative Examples for the epoxy resin composition for encapsulating of the present invention semiconductors of the present invention.
- the examples of the present invention are included for illustrative purposes only and are in no way intended to limit the present invention.
- a three-necked flask having internal capacity of 3-liter equipped with a thermometer, an agitator, and a condenser was charged with the phenol compounds of the kind and the amount shown in Table 1, 1300 g of epichlorohydrin, and 500 g of methoxypropanol. After dissolved uniformly by elevating a temperature to 50° C., 190 g of aqueous solution containing 48.5% by weight of sodium hydroxide was added dropwise over 1 hour. The temperature was gradually elevated during adding dropwise, so that the inside of the system attains to 70° C. at the period of the completion of dropwise addition. After that, reaction was carried out while maintaining the temperature at 70° C. for 30 minutes.
- a three-necked flask having internal capacity of 500-ml equipped with a thermometer, an agitator, and a condenser was charged with the respective epoxy resins prepared in the above-mentioned Preparation Examples 1 to 3 and 5, a cresol novolak type noncrystalline epoxy resin having a softening point of 67° C. which is commercially supplied or a tetramethylbiphenol type crystalline epoxy resin which is commercially supplied, in an amount shown in Table 2, followed by uniformly melting by elevating a temperature to 150° C. Respective molten mixtures were taken out in a vessel, followed by cooling to a room temperature.
- tetramethylbiphenol type crystalline epoxy resin and a brominated bisphenol A type epoxy resin as an epoxy resin
- phenol novolak resin, phenolaralkyl resin, or terpene phenol resin as a curing agent for epoxy resins
- spherical fused silica powder as an inorganic filler
- triphenylphosphine as a curing accelerator
- antimony trioxide as a promotor for flame retardancy
- an epoxy silane as a surface-treating agent for the filler
- carnauba wax as a mold releasing agent
- the spherical fused silica powder was employed in an amount of 87% by weight based on the total amount of the compositions in the Examples 10 to 16 and Comparative Examples 11 to 13, and in an amount of 83% by weight based on the total amount of the compositions in the Comparative Example 10.
- Respective melt mixtures were taken out in the form of sheets, and crushed to obtain respective molding materials after cooling to ordinary temperatures.
- the respective molding materials except Comparative Example 12 were molded at a mold temperature of 180° C. and a molding time of 180 seconds with a low pressure transfer molding machine to prepare respective test pieces, followed by post curing at 180° C. for 8 hours. Further, Spiral Flow was measured in the respective molding materials.
- Table 4 shows the results of Spiral Flow in the respective molding materials, solder crack resistance, moisture absorption ratio, and glass transition temperatures after post curing of the test pieces.
- the respective molding materials in the Examples 10 to 17 are more excellent in a balance between fluidity (that is, a high Spiral Flow) and solder crack resistance compared to the molding materials in the Comparative Examples 10 to 13.
- the epoxy resin composition of the present invention can be crushed at an ordinary temperature, and it is remarkably low in melt viscosity. Further, since the epoxy resin composition for encapsulating semiconductors of the present invention is excellent in fluidity and can provide a cured product having excellent solder crack resistance, it can be advantageously employed in a use of encapsulating semiconductors.
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Abstract
Description
TABLE 1 __________________________________________________________________________ Preparation Example 1 2 3 4 5 6 7 __________________________________________________________________________ Amount (g) of a phenol compound 4,4'-biphenol 188 Cresol novolak resin A *1 240 Cresol novolak resin B *2 170 Cyclopentadienephenol resin *3 340 Terpenephenol resin *4 330 Phenolaralkyl resin *5 340 6,6'-dihydroxy-3,3,3',3'-tetramethyl- 308 1,1'-spirobiindane Bisphenol A 68 Analytical result of Epoxy resins Properties (room temperature) Crystalline Non- Non- Non- Non- Non- Non- Crystalline Crystalline Crystalline Crystalline Crystalline Crystallin e Melting point (° C.) *6 161 -- -- -- -- -- -- Softening point (° C.) *7 -- 52 51 53 44 42 50 Epoxy equivalent 162 205 198 242 233 244 221 Melt viscosity (PS) at 150° C. 0.1 0.7 0.6 0.5 0.3 0.4 0.4 Crushing results Roughly crushing Possible Possible Possible Possible Impossible Impossible Possible Finely crushing Possible Impossible Impossible Impossible Impossible Impossible Impossible __________________________________________________________________________ Note *1: a softening point of 75° C., manufactured by Asahi Yukizai, Ltd. *2: a softening point of 98° C., manufactured by Asahi Yukizai, Ltd. *3: DPR1000 having a softening point of 87° C., manufactured by Mitsui Toatsu Chemicals, INC. *4: YP90 having a softening point of 80° C., manufactured by Yasuhara Chemical, Ltd. *5: XL2253L having a softening point of 71° C., manufactured by Mitsui Toatsu Chemicals, INC. *6: a microscopic method *7: a ball and ring method
TABLE 2 __________________________________________________________________________ Example Comparative Example 1 2 3 1 2 __________________________________________________________________________ Amount (g) of an epoxy resin Epoxy resin in Preparation Example 1 100 40 100 100 Epoxy resin in Preparation Example 2 100 100 Epoxy resin in Preparation Example 3 160 Epoxy resin in Preparation Example 5 100 Cresol novolak type epoxy resin *1 100 Tetramethylbiphenol type epoxy resin *2 100 Analytical result of Epoxy resin Compositions *4 *4 *4 *4 Non- Properties (room temperature) Crystalline Softening point (° C.) *3 *5 *5 *5 *5 46 Epoxy equivalent 181 190 191 184 196 Melt viscosity (PS) at 150 C 0.3 0.2 0.2 0.7 0.4 Crushing results Roughly crushing Possible Possible Possible Possible Impossible Finely crushing Possible Possible Possible Possible Impossible __________________________________________________________________________ Note *1: Epikote 180S65 having a softening point of 67° C. and epoxy equivalent of 212 manufactured by Yuka Shell Epoxy, K.K. *2: Epikote YX4000 having a melting point of 107° C. and epoxy equivalent of 187 manufactured by Yuka Shell Epoxy, K.K. *3: a ball and ring method *4: a mixed state by crystalline and noncrystalline portions *5: incapable of measuring because of a mixed state by crystalline portions
TABLE 3 __________________________________________________________________________ Example 4 5 6 7 8 __________________________________________________________________________ Amount (g) of a phenol compound 4,4'-biphenol 83 94 73 130 71 Cresol novolak resin *1 135 Cyclopentadienephenol resin *2 170 Terpenephenol resin *3 202 Phenolaralkyl resin *4 104 6,6'-dihydroxy-3,3,3',3'-tetramethyl- 192 1,1'-spirobiindane Composition of epoxy resin compositions (% by weight) (a) 4,4'-biphenol type epoxy resin 40 40 30 60 30 (b) noncrystalline epoxy resin 60 60 70 40 70 Analytical result of Epoxy resin compositions Epoxy equivalent 187 203 207 188 202 Melt viscosity (PS) at 150° C. 0.3 0.3 0.2 0.2 0.3 Crushing results Roughly crushing Possible Possible Possible Possible Possible Finely crushing Possible Possible Possible Possible Possible __________________________________________________________________________ Note *1: a softening point of 75° C., manufactured by Asahi Yukizai, Ltd. *2: DPR1000 having a softening point of 87° C. manufactured by Mitsui Toatsu Chemicals, INC. *3: YP90 having a softening point of 80° C. manufactured by Yasuhara Chemical. Ltd. *4: XL2253L having a softening point of 71° C. manufactured by Mitsui Toatsu Chemicals, INC.
TABLE 4 __________________________________________________________________________ Example Comparative Example 10 11 12 13 14 15 16 17 10 11 12 13 __________________________________________________________________________ Formulation of Epoxy resin compositions (parts by weight) Epoxy resin Epoxy resin (composition) Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 *1 *2 Prod. Comp. Ex. 1 Ex. 1 Amount 100 100 100 100 100 100 100 100 100 100 100 100 Brominated epoxy resin *3 10 10 10 10 10 10 10 10 10 10 10 10 Curing agent for an epoxy resin A*4 A*4 B*5 B*5 B*5 C*6 A*4 C*6 A*4 B*5 *6 A*4 Amount 60 57 93 95 88 89 58 1 51 95 112 59 Inorganic filler *7 1220 1200 1450 1460 1410 1420 1210 1430 850 1460 1570 1220 Triphenylphosp hine 1 1 1 1 1 1 1 1 1 1 1 1 Antimony trioxide 10 10 10 10 10 10 10 10 10 10 10 10 Carnauba wax 1 1 1 1 1 1 1 1 1 1 1 1 Epoxy silane *8 1 1 1 1 1 1 1 1 1 1 1 1 Fluidity, Spiral Flow (cm) 80 82 87 85 86 81 81 80 60 83 *9 67 Physical properties after curing Solder crack resistance *10 0/16 0/16 0/16 0/16 0/16 0/16 0/16 0/16 16/16 8/16 *9 4/16 Moisture absorption 0.21 0.21 0.17 0.18 0.16 0.17 0.21 0.17 0.36 0.20 *9 0.23 property (%) *11 Glass transition 151 152 148 147 148 156 141 152 155 117 *9 153 temperature ° C. __________________________________________________________________________ *12 Note *1: orthocresol novolak type epoxy resin (Epikote 180S65 having epoxy equivalent of 212, a trade name by Yuka Shell Epoxy, K.K.) *2: tetramethylbiphenol type epoxy resin (Epikote YX4000 having epoxy equivalent of 187, a trade name by Yuka Shell Epoxy, K.K.) *3: brominated bisphenol A type epoxy resin (Epikote 5050 having epoxy equivalent of 385 and bromine content of 49%, a trade name by Yuka Shell Epoxy, K.K.) *4: A; phenol novolak resin (hydroxyl group equivalent of 103, a softenin point of 85° C., manufactured by GunEi Kagaku, Ltd.) *5: B; phenol aralkyl resin (XL2253L having a hydroxyl group equivalent o 170 and a softening point of 71° C., a trade name by Mitsui Toatsu Chemicals, INC.) *6: C; terpene phenol resin (Epikure MP402 having hydroxyl group equivalent of 175 and a softening point of 125° C., a trade name b Yuka Shell Epoxy, K.K.) *7: spherical fused silica powder (ELSIL BF100, a trade name by Nippon Aerozil, Ltd.) *8: epoxy silane (KBM403, a trade name by ShinEtsu Chemical Co., Ltd.) *9: Incapable of measuring because a molding material was not obtained. *10: There was counted the number of cracked 16 pieces of 44pin- FPP in caused by immersing into a solder bath at 260° C. for 10 seconds after absorbing moisture at 85° C. and 85% RH for 300 hours. *11: moisture absorption ratio after 300 hours at 85° C. and 55% RH. *12: measured from a critical point in a thermal expansion curve with a TMA.
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JP17627797A JP3734602B2 (en) | 1997-05-29 | 1997-05-29 | Epoxy resin composition and epoxy resin composition for semiconductor encapsulation |
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Cited By (12)
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US6255409B1 (en) * | 1998-03-13 | 2001-07-03 | Sumitomo Chemical Co., Ltd. | Epoxy resin composition and resin-encapsulated semiconductor device |
EP1277798A2 (en) * | 2001-07-19 | 2003-01-22 | San-Ei Kagaku Co. Ltd. | Thermosetting resin composition |
US6534912B1 (en) * | 1998-05-20 | 2003-03-18 | Futaba Corporation | Active matrix drive fluorescent display device and method for manufacturing same |
US20100016498A1 (en) * | 2005-05-10 | 2010-01-21 | Masashi Kaji | Epoxy resin composition and cured article thereof |
WO2010016987A1 (en) * | 2008-08-05 | 2010-02-11 | Dow Global Technologies Inc. | Production of solid epoxy resin |
US20120115281A1 (en) * | 2010-11-10 | 2012-05-10 | Nitto Denko Corporation | Method of manufacturing semiconductor device |
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US20130184377A1 (en) * | 2010-07-30 | 2013-07-18 | Dic Corporation | Curable resin composition, cured product thereof, phenol resin, epoxy resin, and semiconductor encapsulating material |
US8937145B2 (en) | 2009-12-02 | 2015-01-20 | Dow Global Technologies Llc | Epoxy resin compositions |
US9006312B2 (en) | 2009-12-02 | 2015-04-14 | Dow Global Technologies Llc | Composite compositions |
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JP2001114983A (en) * | 1999-10-14 | 2001-04-24 | Toto Kasei Co Ltd | Epoxy resin composition and production method of epoxy resin |
JP4560871B2 (en) * | 2000-02-23 | 2010-10-13 | 住友ベークライト株式会社 | Epoxy resin composition and semiconductor device |
JP4696372B2 (en) * | 2001-02-14 | 2011-06-08 | 住友ベークライト株式会社 | Epoxy resin composition and semiconductor device |
JP4609692B2 (en) * | 2003-09-12 | 2011-01-12 | Dic株式会社 | Epoxy resin, method for producing epoxy resin, epoxy resin composition and cured product thereof |
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US5414058A (en) * | 1990-05-28 | 1995-05-09 | Somar Corporation | Powder coating composition comprising conventional epoxides with crystalline epoxides and curing agents |
US5312878A (en) * | 1991-10-07 | 1994-05-17 | Shin-Etsu Chemical Company, Limited | Naphthalene containing epoxy resin cured with a dicyclopentadiene phenolic resin |
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US6255409B1 (en) * | 1998-03-13 | 2001-07-03 | Sumitomo Chemical Co., Ltd. | Epoxy resin composition and resin-encapsulated semiconductor device |
US6534912B1 (en) * | 1998-05-20 | 2003-03-18 | Futaba Corporation | Active matrix drive fluorescent display device and method for manufacturing same |
EP1277798A2 (en) * | 2001-07-19 | 2003-01-22 | San-Ei Kagaku Co. Ltd. | Thermosetting resin composition |
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US20030162898A1 (en) * | 2001-07-19 | 2003-08-28 | Kiyoshi Sato | Thermosetting resin composition |
US6812299B2 (en) | 2001-07-19 | 2004-11-02 | San-Ei Kagaku Co., Ltd. | Composition of epoxy resin-unsaturated acid adduct, (meth)acrylate and crystallizable epoxy resin |
US20050019582A1 (en) * | 2001-07-19 | 2005-01-27 | Kiyoshi Sato | Thermosetting resin composition |
US7410673B2 (en) | 2001-07-19 | 2008-08-12 | San-Ei Kagaku Co., Ltd. | Smooth board and process for preparing a smooth board |
US20100016498A1 (en) * | 2005-05-10 | 2010-01-21 | Masashi Kaji | Epoxy resin composition and cured article thereof |
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US9340702B2 (en) | 2009-12-02 | 2016-05-17 | Blue Cube Ip Llc | Coating compositions |
US20130184377A1 (en) * | 2010-07-30 | 2013-07-18 | Dic Corporation | Curable resin composition, cured product thereof, phenol resin, epoxy resin, and semiconductor encapsulating material |
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US20170213625A1 (en) * | 2016-01-25 | 2017-07-27 | Minebea Co., Ltd. | Rare earth bonded magnet |
US10629342B2 (en) * | 2016-01-25 | 2020-04-21 | Minebea Mitsumi Inc. | Rare earth bonded magnet |
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Also Published As
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JPH10330600A (en) | 1998-12-15 |
JP3734602B2 (en) | 2006-01-11 |
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